CN103372449A - Hydrotreating catalyst, and preparation method and application thereof - Google Patents
Hydrotreating catalyst, and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a hydrotreating catalyst, and preparation and application thereof. The catalyst contains a boron-containing alumina support, at least one metal component selected from Group VIII and at least one metal component selected from Group VIB. The invention is characterized in that the Group VIB metal component exists in the form of metal oxide, and the Group VIII metal component exists in the form of metal salt. Compared with the prior art, the hydrotreating properties of the catalyst provided by the invention are obviously improved. The catalyst can be applied to various hydrocarbon oil hydrotreating processes.
Description
Technical field
The present invention relates to a kind of hydrotreating catalyst, its preparation and application.
Background technology
The hydrofinishing of hydrocarbon raw material or hydrotreatment are a kind of technical process of generally using in the petroleum refining industry, and its effect mainly is to remove the impurity such as sulphur in the hydrocarbon feed, nitrogen, metal, aromatic hydrocarbons, carbon residue.By hydrotreatment, perhaps can directly obtain the light-end products that clean, for example diesel oil is carried out can obtaining the clean diesel product after the hydrofinishing; Perhaps can improve the character of hydrocarbon feed, for example the FCC raw material be carried out preliminary treatment, the improved hydrocarbon feed of character is re-used as the charging of FCC process, to improve the efficient of FCC process.Employed hydrogenation catalyst is made of the carrier that comprises group vib (such as molybdenum or tungsten) and group VIII metal (such as cobalt or nickel) component usually in the hydrotreatment process.Catalyst carrier for hydrgenating adopts aluminium oxide more, in order to improve the performance of catalyst, often introduces other modifying element in aluminium oxide, for example prepares the alumina support of boracic.
Traditional Hydrobon catalyst or hydrotreating catalyst generally contain group vib metal oxide and VIII family metal oxide, catalyst usually carries out one or many by the solution that will contain group vib metallic compound and/or VIII family metallic compound with carrier and contacts, and method dry by one or many and roasting prepares again.
Patent ZL96194541 discloses a kind of hydrogenation catalyst, this catalyst contains with the VIII family metal oxide of carrier supported and VI family metal oxide, the additive of selected at least a compound in the compound of other also self-contained at least two hydroxyls of this catalyst and 2-10 carbon atom and the polyethers of these compounds, wherein VIII family metallic compound and VI family metallic compound are the form of oxide.
Patent ZL89109140 discloses a kind of catalyst for hydrorefining distillate oil and preparation method thereof.Described catalyst contains three kinds of active metal components of W-Mo-Ni, take silica-alumina as carrier, adds boron additive.The preparation method of described catalyst comprises and prepares respectively the W-Ni aqueous solution and Mo-B ammonia spirit, adopts to spray method active component and auxiliary agent are added on the carrier, sprays all to make catalyst through super-dry and roasting afterwards at every turn.
Patent application CN200710118009 discloses a kind of heavy oil hydrogenating treatment catalyst and preparation method thereof.Described catalyst contains boron-containing alumina carrier and at least a VIB and at least a metal component that is selected from group VIII of being selected from, the sintering temperature of described boron-containing alumina carrier is 600-950 ℃, after introducing reactive metal, boron-containing alumina carrier makes catalyst through roasting, wherein, the content of boron is the 0.3-5 % by weight.
Patent ZL200310104915 provides a kind of catalyst for hydrogen refining of paraffin wax and preparation method thereof, comprises at first preparing novel carrier γ-Al
2O
3, the halogen compounds of adding boron-containing compound or boracic makes it have better surface texture in the carrier preparation process, more is conducive to the dispersion of reactive metal (Mo, Ni).Then with this carrier of Mo-Ni-P solution impregnation, and drying, the steps such as roasting make Mo-Ni-P/B
2O
3-Al
2O
3Catalyst, wherein, the content of boron is the 3-10 % by weight.
Patent ZL00110464 relates to a kind of hydrorefining catalyst for hydrocarbon and preparation method thereof, and described catalyst is with γ-Al
2O
3Be carrier, group vib and group VIII metal are active component, also contain simultaneously auxiliary agent boron.This catalyst adopts a kind of dipping solution that contains simultaneously group vib, group VIII metal component, organic carboxyl acid and polyalcohol mixed twine mixture and auxiliary agent boron through dipping, drying and roasting preparation, and wherein, the content of boron is the 0.5-10 % by weight.
Patent application CN200910187912 discloses a kind of hydrotreating catalyst and preparation method thereof, and described catalyst comprises boron-containing alumina carrier and VIB, VIII family metal component.The preparation method of described catalyst comprise boracic aluminium hydroxide preparation, boron-containing alumina carrier preparation and on boron-containing alumina carrier the supported active metal, and drying and 400-750 ℃ of roasting make catalyst, wherein, the content of boron is the 0.5-8 % by weight.
Document (" NiW/B
2O
3-Al
2O
3The relation of the preparation of catalyst and pyridine hydrodenitrogenationactivity activity ", Yinshan Mountains academic periodical (natural science edition), 3 phases of 1998,14 volumes, 20 pages) reported a kind of B
2O
2-Al
2O
3The preparation of carrier loaded NiW catalyst comprises and adopts infusion process to introduce boron oxide at aluminium oxide, floods afterwards Ni-W solution and carries out drying and roasting.
In the prior art, also have some reports to relate to the catalyst preparation technology that preparation process does not comprise calcination steps, vib metal and VIII family metal obviously exist with the form of non-oxidized substance in these catalyst.Even in preparation process, adopted metal oxide for example molybdenum oxide because its solubility extremely low in the aqueous solution, thereby also need to be converted into other compound effects salt or complex compound or the heteropoly acid etc. of solubility as precursor.
Patent ZL200710176737 discloses a kind of preparation method who exempts from the petroleum distillate oil hydrogenation catalysts of roasting, and the method comprises: (1) joins organic sequestering agent in the deionized water, and organic sequestering agent is dissolved fully; (2) add the salt that contains group vib and VIII family metal; (3) obtain the maceration extract of pH value 6-8, according to equi-volume impregnating dipping catalyst carrier for hydrgenating, 100-150 ℃ of drying obtains described catalyst.Obviously, group vib and VIII family metal all exist with the slaine form in the described catalyst.
Patent ZL200380106678 discloses a kind of catalyst for hydrotreatment light oil, this catalyst comprises on the inorganic oxide carrier at least a metal that is selected from periodic table VI family metal, at least a metal that is selected from periodic table group VIII metal of 1-15 % by weight and the phosphorus of 1.5-8 % by weight in the 10-40 % by weight of oxide, and in the carbon of the 2-14 % by weight of carbon, the preparation of this catalyst comprises that the solution that will contain said components is carried on the inorganic oxide carrier, carries out drying afterwards under 200 ℃ or lower temperature.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of hydrotreating catalyst and preparation and application new, that performance is further improved.
The present inventor finds under study for action, compare with unfired catalyst with the metal oxide catalyst that roasting obtains, vib metal exists with oxide form in catalyst, and VIII family metal is when existing with the slaine form, and catalyst has higher activity.
The present invention relates to following invention:
1, a kind of hydrotreating catalyst, contain boron-containing alumina carrier and at least a VIII of being selected from family and at least a metal component that is selected from group vib, it is characterized in that described group vib metal component exists with the form of metal oxide, described VIII family metal component exists with the form of slaine.
2, according to 1 described catalyst, take catalyst as benchmark and with oxide, the content of described VIII family metal component is the 1-10 % by weight, and the content of group vib metal component is the 5-40 % by weight.
3, according to 2 described catalyst, take catalyst as benchmark and with oxide, the content of described VIII family metal component is the 1.5-7 % by weight, and the content of group vib metal component is the 7-35 % by weight.
According to 1 described catalyst, it is characterized in that 4, described group vib metal component is selected from one or more among Cr, Mo, the W, described VIII family metal component is selected from one or more among Fe, Co, the Ni.
According to 4 described catalyst, it is characterized in that 5, described group vib metal is Mo and/or W, described VIII family metal component is Co and/or Ni.
According to 1 described catalyst, it is characterized in that 6, described slaine is selected from the inorganic salts of VIII family metal component or one or more in the organic salt.
According to 6 described catalyst, it is characterized in that 7, described inorganic salts are selected from one or more in carbonate, subcarbonate, the nitrate.
According to 6 described catalyst, it is characterized in that 8, described organic salt is organic carboxylate.
According to the described catalyst of 1-8, it is characterized in that 9, described catalyst also contains one or more auxiliary agents that are selected from phosphorus, fluorine, the silicon, in element and take catalyst as benchmark, the content of described auxiliary agent is no more than 10 % by weight.
According to the described catalyst of 1-8, it is characterized in that 10, described catalyst also contains organic additive, take described catalyst as benchmark, and in carbon, the content of described organic additive is no more than 10 % by weight.
11, catalyst according to claim 1 is characterized in that, take described carrier as benchmark, the content of boron oxide is the 0.5-10 % by weight in the described boron-containing alumina carrier.
12, catalyst according to claim 11 is characterized in that, take described carrier as benchmark, the content of boron oxide is the 1-7 % by weight in the described boron-containing alumina carrier.
13, a kind of preparation method of hydrogenation catalyst comprises:
(1) with the solution impregnation boron-containing alumina carrier of the compound that contains the group vib metal, carry out afterwards drying and roasting, the condition of described roasting makes the described compound that contains the group vib metal be enough to be converted into oxide;
(2) product that obtains with the solution impregnation step (2) that contains VIII family slaine carries out drying afterwards, and the condition deficiency of described drying is so that VIII family slaine is decomposed into oxide.
According to 13 described methods, it is characterized in that 14, the baking temperature of described step (1) is 80-300 ℃, be 1-12 hour drying time, and described sintering temperature is 350-550 ℃, and roasting time is 2-10 hour; The baking temperature of described step (2) is 30-250 ℃, and be 1-8 hour drying time.
According to 13 described methods, it is characterized in that 15, the baking temperature of described step (1) is 100-250 ℃, be 2-8 hour drying time, and described sintering temperature is 400-500 ℃, and roasting time is 3-6 hour; The baking temperature of described step (2) is 60-200 ℃, and be 2-6 hour drying time.
According to 13 described methods, it is characterized in that 16, described method also comprises introduces the step that is selected from one or more auxiliary agents in phosphorus, fluorine, the silicon.
According to 13 described methods, it is characterized in that 17, described method also comprises the step of introducing organic additive.
18, a kind of method for hydrotreating hydrocarbon oil is included under the hydrotreatment reaction condition, with hydrocarbon ils and catalyst haptoreaction, it is characterized in that, described catalyst is the described catalyst of aforementioned 1-12 any one.
According to catalyst provided by the invention, the described VIII of being selected from family and the content that is selected from the metal component of group vib are the usual content of hydrotreating catalyst, for example, take catalyst as benchmark and with oxide, described catalyst contains the VIII family metal component of 1-10 % by weight, the group vib metal component of 5-40 % by weight; The VIII family metal component that preferably contains the 1.5-7 % by weight, the group vib metal component of 7-35 % by weight.Described group vib metal is selected from one or more among Cr, Mo or the W, preferred Mo and/or W, and described VIII family metal component is selected from one or more among Fe, Co or the Ni, preferred Co and/or Ni.
Take described carrier as benchmark, the content of boron oxide is the 2-35 % by weight in the preferred boron-containing alumina, and the content of aluminium oxide is the 65-98 % by weight; Further the content of preferential oxidation boron is the 3-30 % by weight, and the content of aluminium oxide is the 70-97 % by weight.
Described boron-containing alumina has specific surface and the pore volume of conventional boron-containing alumina carrier, and the specific surface of preferred boron-containing alumina is 100-350 rice
2/ gram, more preferably 120-300 rice
2/ gram, the pore volume of preferred boron-containing alumina is 0.4-1.2 ml/g, more preferably 0.5-1.0 ml/g.
Described boron-containing alumina carrier can be commercially available commodity, or adopts any one prior art preparation, such as infusion process, sol-gel process and coprecipitation etc.A method that preferably prepares boron-containing alumina, be with the precursor of aluminium oxide and/or aluminium oxide mix with the precursor of boron oxide and/or boron oxide, roasting obtains.The mixing of boron-containing compound and aluminum contained compound can be undertaken by mixing, soak, flood, deposit, be total to the modes such as glue, precipitation such as kneading, stone roller.In case of necessity, boron-containing compound can be scattered in the middle of the solvent, mix with aluminum contained compound again.Described sintering temperature is 400-650 ℃, and roasting time is 1-10 hour, and preferred sintering temperature is 450-620 ℃, and roasting time is 2-8 hour.The consumption of the boron-containing compound of selecting should be so that final carrier contains the boron oxide of aequum.
Described boron-containing compound can be selected from one or more among boron oxide, boric acid, ammonium hydrogen borate, tetraboric acid ammonium, ammonium pentaborate, Boratex, ammonium fluoroborate, boron trifluoride, the methyl borate.
Described aluminum contained compound can be selected from one or more the mixture among aluminium oxide, hibbsite, monohydrate alumina and the amorphous hydroted alumina, or one or more the mixture among hibbsite, monohydrate alumina and the amorphous hydroted alumina of siliceous, titanium, magnesium, boron, zirconium, thorium, niobium, rare earth.
According to catalyst provided by the invention, can also contain any material that the performance that the invention provides catalyst maybe can be improved catalyst performance provided by the invention that do not affect.As containing one or more in the components such as phosphorus, fluorine, silicon, in element and take catalyst as benchmark, the content of above-mentioned auxiliary agent is no more than 10 % by weight, is preferably the 0.5-6 % by weight.
According to catalyst provided by the invention, can also contain organic additive, take described catalyst as benchmark, and in carbon, the content of described organic additive is no more than 10 % by weight, further preferably is no more than 6 % by weight.
Described organic additive is selected from one or more that contain in oxygen and/or the nitrogenous organic matter.Described oxygenatedchemicals is selected from one or more in Organic Alcohol, the organic acid, and organic compounds containing nitrogen is selected from one or more in organic amine, the organic ammonium salt.Particularly, be selected from oxygen containing organic matter and be selected from ethylene glycol, glycerine, polyethylene glycol (molecular weight is 200-1500), diethylene glycol, butanediol, acetic acid, maleic acid, oxalic acid, aminotriacetic acid, 1, in 2-CDTA, citric acid, tartaric acid, the malic acid one or more, wherein preferred ethylene glycol, glycerine, polyethylene glycol and citric acid; Nitrogenous organic matter is selected from one or more in ethylenediamine, diethylenetriamines, 1,2-diaminocyclohexane tetraacetic acid, amion acetic acid, NTA, EDTA and the ammonium salt thereof, wherein preferred EDTA and NTA.Described organic additive also can comprise simultaneously and contains organic pure and mild organic acid.
According to method for preparing catalyst provided by the invention, be enough to the described at least a VIII of being selected from family and at least a metal component that is selected from group vib is carried on the described boron-containing alumina carrier and described group vib metal component is existed with the form of metal oxide, under the prerequisite that described VIII family metal component exists with the form of slaine, concrete operation step is not particularly limited.For example, the method that the described at least a VIII of being selected from family and at least a metal component that is selected from group vib is carried on the described carrier is infusion process.Described dipping can be excessive liquid dipping, the saturated dipping in hole according to maceration extract consumption difference, and the mode difference that realizes according to dipping can be infusion method dipping, spray impregnating.By the regulation and control to concentration, consumption or the carrier consumption of dipping solution, can prepare the described catalyst of specifying content, it is intelligible that this is that those skilled in the art hold.
According to method for preparing catalyst provided by the invention, described group vib metallic compound is selected from one or more in the soluble compound of these metals, for example, can be in silico-tungstic acid, silicotungstate, phosphomolybdic acid, phosphomolybdate, molybdate, paramolybdate, tungstates, metatungstate, the ethyl metatungstate one or more.
Described group VIII slaine is at least a of inorganic acid salt or organic salt, described inorganic salts are selected from one or more in the partially decomposed product of nitrate, carbonate, subcarbonate, hypophosphites, phosphate, sulfate, chloride and these salts, preferably, be selected from nitrate, carbonate or the subcarbonate one or more.Described organic salt to be organic matter with VIII family metal be combined salt or the soluble complexes that generates, described organic matter can be organic base, organic carboxyl acid, amine, ketone, ethers, alkyls, is preferably organic carboxylate.
According to method for preparing catalyst provided by the invention, after the introducing group vib metal of step (1), need carry out drying and roasting, the method for described drying and condition can be usual method and conditions in the catalyst preparation, and there is no particular limitation to this present invention.For example, described drying means is the method for heat drying, and its baking temperature can be 80-300 ℃, and be 1-12 hour drying time, and preferred baking temperature is 100-250 ℃, and be 2-8 hour drying time.Described roasting is so that the group vib metallic compound of load can be decomposed into oxide is prerequisite, and preferred sintering temperature is 350-to 550 ℃, and more preferably 400-500 ℃, roasting time is 2-10 hour, is preferably 3-6 hour.Atmosphere for roasting does not have special requirement, can be the mixture of air, oxygen or nitrogen or above-mentioned gas, is preferably air.
In step (2), introduce after the group VIII metal, need to carry out drying, selected drying condition answers deficiency so that VIII family slaine or the complex compound of load are decomposed into oxide, adoptable baking temperature is 30-250 ℃, be preferably 60-200, more preferably 70-180 ℃, 1-8 hour drying time, preferred 2-6 hour.Drying is preferably carried out under air atmosphere.
According to preparation method provided by the invention, during one or both adjuvant components in also containing components such as being selected from phosphorus, fluorine, silicon in the described catalyst, also comprise and introduce the step that is selected from one or more components in the components such as phosphorus, fluorine, silicon, the described introducing method that is selected from the components such as phosphorus, fluorine, silicon can pass through number of ways, as can be that compound with auxiliary agent as described in containing directly mixes with zirconium-containing compound, aluminum contained compound or zirconium aluminium compound, moulding and roasting; Can be the compound that to contain described auxiliary agent and contact with described carrier after the compound that contains the hydrogenation active metals component is mixed with mixed solution; Can also be to contact and roasting with described carrier behind the independent obtain solution of the compound that contains auxiliary agent.When auxiliary agent and hydrogenation active metals are introduced described carrier respectively, preferably at first auxiliary compound solution contacts with described carrier and roasting with containing, contact with the solution of the compound that contains the hydrogenation active metals component more afterwards, for example pass through the method for dipping, described sintering temperature is 250-600 ℃, be preferably 350-500 ℃, roasting time is 2-8 hour, is preferably 3-6 hour.
According to preparation method provided by the invention, when catalyst of the present invention further contains organic compound, also comprise the step of introducing organic compound, described organic compound can be introduced together with the group VIII metal, also can after introducing the group VIII metal, introduce, and carry out drying, and preferably organic matter and group VIII metal are mixed with mixed solution and introduce simultaneously by the mode of dipping, carry out afterwards drying.The selection of described baking temperature and time except deficiency so that VIII family slaine or complex compound decompose, also should allow in catalyst, to keep most of organic matter of introducing, for example keep the organic matter more than 50%, more preferably, keep the organic matter more than 70%.Its method can be any one method that can realize above-mentioned purpose in the prior art.For example, heat drying, drying under reduced pressure and add the methods such as thermal drying under reduced pressure.When described drying means was heat drying, preferred baking temperature was no more than 250 ℃, further preferably is no more than 200 ℃, is more preferably and is no more than 180 ℃.For example, one preferred embodiment in, described baking temperature is 70 ℃-180 ℃.
According to the present invention, when preparation contains the described catalyst of organic compound, in carbon and take described catalyst as benchmark, preferably pass through to select the introducing amount of described organic compound so that in the final catalyst, the content of described organic additive is no more than 10 % by weight, further preferably is no more than 6 % by weight.
According to the conventional method in this area, described hydrotreating catalyst is before using, usually can be in the presence of hydrogen, under 140-370 ℃ temperature, carry out presulfurization with sulphur, hydrogen sulfide or sulfur-bearing raw material, this presulfurization can be carried out outside device also can original position sulfuration in device, and the active metal component of its load is converted into the metal sulfide component.
In hydrotreating method provided by the invention, to described hydroconversion condition without any special restriction, can adopt common reaction condition, for example can enumerate reaction temperature 200-420 ℃, more preferably 220-400 ℃, pressure 2-18 MPa, 2-15 MPa more preferably, liquid hourly space velocity (LHSV) 0.3-10 hour
-1, more preferably 0.3-5 hour
-1, hydrogen to oil volume ratio 50-5000,50-4000 more preferably.
The device of described hydrotreatment reaction can be enough to make described feedstock oil to carry out under the hydrotreatment reaction condition with in the catalytic reaction dress of the described catalyst device any, for example, at described fixed bed reactors, carry out in moving-burden bed reactor or the fluidized bed reactor.
Adopt hydrotreating method provided by the invention can directly process all kinds of hydrocarbon oil crude materials, so that it is carried out hydrofinishing, hydro-upgrading or hydrocracking.Described hydrocarbon oil crude material can be various mineral oil or artificial oil or biodiesel or their mixed fraction oil, such as be selected from crude oil, distillate, solvent-refined oil, slack wax, sweat oil, Fischer-Tropsch synthesis oil, liquefied coal coil, frivolous coal tar and the heavy deasphalted oil one or more.
Compared with prior art, the invention provides catalyst and have higher hydrotreatment activity.For example, under the hydrogenation active metals content and the identical situation of carrier of catalyst, CoMo catalyst provided by the invention (contains MoO
310 % by weight, the NiO2.0 % by weight), to compare with the CoMo catalyst of exempting from the method for roasting preparation with the CoMo catalyst that adopts the method for roasting preparation, the residuum hydrodesulfurization rate can improve respectively 1.1% and 1.9%.
The specific embodiment
Following example will the present invention will be further described, but therefore do not limit content of the present invention.
Carbon content in the catalyst adopts analyses, and other components are except specifying, all adopt x-ray fluorescence spectrometry, the composition of all catalyst is provided by table 1.
Embodiment 1
The preparation of the used boron-containing alumina carrier BA of this example explanation catalyst of the present invention:
First with the 1000 gram aluminum hydroxide solid elastomer powder (boehmites that Sinopec catalyst Chang Ling branch company produces, butt 70%) mixes with 33 gram sesbania powder, again with this mixture and boronic acid containing (chemical reagents corporation of Beijing Jin Hui the Pacific-Asian production, analyze pure) 870 milliliters of the aqueous solution of 52 grams, 25 milliliters of nitric acid (concentration 65-68%, analyze pure, chemical plant, Gansu Province, west, Shantou) mixes, it is even to continue kneading at double screw banded extruder, be extruded into afterwards the butterfly bar of 1.3 millimeters of ф, wet bar is through 120 ℃ of dryings after 4 hours, in 600 ℃ of roastings 3 hours, obtain boron-containing alumina carrier BA.Adopt x-ray fluorescence method to measure the composition of ZA-2, in oxide and take described carrier as benchmark, boron oxide content is 4.0 % by weight.
Adopt BET N
2Absorption method is analyzed the BA carrier, and the specific area of this carrier is 244 meters squared per gram, 0.62 ml/g of pore volume.
Embodiment 2-4 illustrates catalyst provided by the invention and preparation thereof
Comparative Examples 1-6 explanation comparative catalyst and preparation thereof
The employed raw material sources of Kaolinite Preparation of Catalyst are as follows: ammonium paramolybdate, Anqing moon metallurgy of copper chemical industry Co., Ltd product, technical grade; Ammonium metatungstate, Zhuzhou diamond tungsten product Co., Ltd product, technical grade; Nickel nitrate, Beijing Yili Fine Chemicals Co., Ltd.'s product is analyzed pure; Basic nickel carbonate, Yixing Xu Chi chemical industry Co., Ltd product, chemical pure; Cobalt nitrate, Beijing Yili Fine Chemicals Co., Ltd. analyzes pure; Phosphoric acid, Beijing Chemical Plant's product, analyze pure, 85% concentration; Ammoniacal liquor, 25% concentration, Beijing Chemical Plant's product is analyzed pure; Citric Acid Mono, Beijing Chemical Plant's product is analyzed pure; Ammonium fluoride, chemical plant, Jinan product is analyzed pure.
Embodiment 2
Get BA carrier 150 grams, flooded 2 hours with 120 milliliters of aqueous solution that contain ammonium paramolybdate 25.4 grams, ammoniacal liquor 5.0 grams, in 120 ℃ of dryings 4 hours, 450 ℃ of roastings 4 hours, what make the load molybdenum oxide contains the molybdenum carrier, contain the molybdenum carrier 2 hours with 90 milliliters of aqueous solution dippings that contain cobalt nitrate 13.8 gram afterwards, in 120 ℃ of dryings 4 hours, make catalyst C-1.Take catalyst weight as benchmark, adopt the chemical composition among the x-ray fluorescence method mensuration catalyst C-1, measurement result is listed in table 1 (together lower).
Comparative Examples 1
Get BA carrier 150 gram, flooded 2 hours with 120 milliliters of aqueous solution that contain ammonium paramolybdate 25.4 grams, cobalt nitrate 13.8 grams, ammoniacal liquor 5.0 grams, in 120 ℃ of dryings 4 hours, 450 ℃ of roastings 4 hours obtained comparative catalyst DC-1A.
Comparative Examples 2
Get BA carrier 150 gram, contain ammonium paramolybdate 25.4 grams, cobalt nitrate 13.8 grams with 120 milliliters, the aqueous solution of ammoniacal liquor 5.0 grams flooded 2 hours, in 120 ℃ of dryings 4 hours, obtained comparative catalyst DC-1B.
Embodiment 3
Get BA carrier 150 grams, flooded 2 hours with 120 milliliters of aqueous solution that contain ammonium paramolybdate 38.7 grams, phosphatase 79 .5 gram, in 120 ℃ of dryings 4 hours, 450 ℃ of roastings 4 hours, what make the load molybdenum oxide contains the molybdenum carrier, contain the molybdenum carrier 2 hours with the 78 milliliters of dippings of the aqueous solution that contain basic nickel carbonate 11.5 gram, Citric Acid Mono 22.0 grams afterwards, in 120 ℃ of dryings 4 hours, obtain catalyst C-2.
Comparative Examples 3
Get BA carrier 150 grams, flooded described carriers 2 hours with 120 milliliters of the aqueous solution that contains ammonium paramolybdate 38.7 grams, basic nickel carbonate 11.5 grams, phosphatase 79 .5 gram and Citric Acid Mono 22.0 grams, in 120 ℃ of dryings 4 hours, 450 ℃ of roastings 4 hours obtained comparative catalyst DC-2A.
Comparative Examples 4
Get BA carrier 150 gram, with 120 milliliters of described carriers of dipping of the aqueous solution that contain ammonium paramolybdate 38.7 grams, basic nickel carbonate 11.5 grams, phosphatase 79 .5 gram and Citric Acid Mono 22.0 grams 2 hours, in 120 ℃ of dryings 4 hours, obtain comparative catalyst DC-2B.
Embodiment 4
Get BA carrier 150 gram, with 120 milliliters of dippings of the aqueous solution of fluorinated ammonium 18.8 grams 2 hours, in 120 ℃ of oven dry 2 hours, 450 ℃ of roastings 3 hours obtained fluorine-containing carrier.
With 105 milliliters of aqueous solution dippings that contain ammonium metatungstate 71.0 gram 2 hours, in 120 ℃ of oven dry 2 hours, 450 ℃ of roastings 3 hours made the tungstenic carrier of load tungsten oxide.
With 60 milliliters of above-mentioned tungstenic carriers of dipping of the aqueous solution that contains nickel nitrate 27.5 gram, in 150 ℃ of dryings 4 hours, obtain catalyst C-3.
Comparative Examples 5
Get BA carrier 150 gram, with 120 milliliters of dippings of the aqueous solution of fluorinated ammonium 18.8 grams 2 hours, in 120 ℃ of oven dry 2 hours, 450 ℃ of roastings 3 hours obtained fluorine-containing carrier.
With 105 milliliters of above-mentioned fluorine-containing carriers of dipping of the aqueous solution that contains ammonium metatungstate 71.0 gram, nickel nitrate 27.5 grams 2 hours, in 120 ℃ of dryings 4 hours, 450 ℃ of roastings 4 hours obtained comparative catalyst DC-3A.
Comparative Examples 6
Get BA carrier 150 gram, with 120 milliliters of dippings of the aqueous solution of fluorinated ammonium 18.8 grams 2 hours, in 120 ℃ of oven dry 2 hours, 450 ℃ of roastings 3 hours obtained fluorine-containing carrier.
With 105 milliliters of above-mentioned fluorine-containing carriers of dipping of the aqueous solution that contains ammonium metatungstate 71.0 gram, nickel nitrate 27.5 grams 2 hours, in 150 ℃ of dryings 4 hours, obtain comparative catalyst DC-3B.
Table 1
Embodiment 5-7 explanation the invention provides the effect of catalyst.
Comparative Examples 7-12 explanation comparative catalyst's effect.
Embodiment 5
The residuum hydrodesulfurization performance of present embodiment explanation catalyst C-1 of the present invention.
Catalyst breakage is become the 2-4 mm granules, and evaluate catalysts C-1 on 100 milliliters of hydrogenation plants, reaction raw materials oil adopt normal slag in the sand, and sulfur content is 4.53%, and nitrogen content is 0.30%, and metal (nickel+vanadium) total amount is 101ppm.Reaction condition is: 390 ℃ of reaction temperatures, hydrogen dividing potential drop 14 MPas, volume space velocity 0.5h
-1
The assay method of sulphur is GB/T 17040-2008.
Calculate desulfurization degree according to following formula:
The evaluation result of catalyst sees Table 2.
Comparative Examples 7
The residuum hydrodesulfurization handling property of this Comparative Examples explanation reference catalyst DC-1A.
According to the method evaluation comparative catalyst DC-1A of embodiment 5, reaction result sees Table 2.
Comparative Examples 8
The residual oil wax oil hydrogenation desulfurization performance of this Comparative Examples explanation reference catalyst DC-1B.
According to the method evaluation comparative catalyst DC-1B of embodiment 5, reaction result sees Table 2.
Table 2
| Catalyst | Desulfurization degree/% | |
| Embodiment 5 | C-1 | 87.9 |
| Comparative Examples 7 | DC-1A | 86.8 |
| Comparative Examples 8 | DC-1B | 86.0 |
Table 2 is the result show, C-1 catalyst provided by the invention has better residuum hydrodesulfurization performance than Comparative Examples catalyst DC-1A and DC-1B.
Embodiment 6
Present embodiment illustrates the wax oil hydrogenation nitrogen removal performance of catalyst C-2 provided by the invention.
Catalyst breakage is become the 2-4 mm granules, and evaluate catalysts C-2 on 100 milliliters of hydrogenation plants, raw materials used oil are Middle East VGO, and sulfur content is 1.8%, and nitrogen content is 0.11%, and density is 0.9078g/cm
3Reaction condition is: 375 ℃ of reaction temperatures, hydrogen dividing potential drop 8.0 MPas, volume space velocity 1.0h
-1The hydrodenitrogenationactivity activity of catalyst is calculated by 1 order reaction, and related computing formula is as follows, and hydrodenitrogenationactivity activity is calculated by 1 order reaction, and computing formula is as follows.
The nitrogen determination method is SH/T 0657-2007.
Comparative Examples 9
The wax oil hydrogenation nitrogen removal performance of this Comparative Examples explanation reference catalyst DC-2A.
According to the method evaluation reference catalyst DC-2A of embodiment 6, reaction result is listed in table 3, take the activity of DC-2A catalyst as 100.
Comparative Examples 10
The wax oil hydrogenation nitrogen removal performance of this Comparative Examples explanation reference catalyst DC-2B.
According to the method evaluation reference catalyst DC-2B of embodiment 6, reaction result is listed in table 3.
Table 3
| Catalyst | Relative denitrification activity | |
| Embodiment 6 | C-2 | 118 |
| Comparative Examples 9 | DC-2A | 100 |
| Comparative Examples 10 | DC-2B | 111 |
Table 3 is the result show, C-2 catalyst wax oil hydrodenitrogeneration performance provided by the invention is better than Comparative Examples catalyst DC-2A and DC-2B.
Embodiment 7
Present embodiment illustrates that the residual hydrogenation of catalyst C-3 provided by the invention takes off the carbon residue performance.Feedstock oil adopts the normal slag in the Middle East, and sulfur content is 4.7%, and nitrogen content is 0.29%, carbon residue 12.6%.Reaction condition is: 385 ℃ of reaction temperatures, hydrogen dividing potential drop 15.0 MPas, volume space velocity 0.5h
-1The analytical method of carbon residue is GB/T17144-1997.Reaction result is listed in table 4.
Take off carbon yield according to following formula calculating.
Comparative Examples 11
The residual hydrogenation of this Comparative Examples explanation reference catalyst DC-3A takes off the carbon residue performance.
According to the method evaluation reference catalyst DC-3A of embodiment 7, reaction result is listed in table 4.
Comparative Examples 12
The residual hydrogenation of this Comparative Examples explanation reference catalyst DC-3B takes off the carbon residue performance.
According to the method evaluation reference catalyst DC-3B of embodiment 7, reaction result is listed in table 4.
Table 4
| Catalyst | Take off carbon yield/% | |
| Embodiment 7 | C-3 | 56.2 |
| Comparative Examples 11 | DC-3A | 55.8 |
| Comparative Examples 12 | DC-3B | 54.6 |
Table 4 is the result show, C-3 catalyst residual hydrogenation provided by the invention takes off the carbon residue activity and is higher than Comparative Examples catalyst DC-3A and DC-3B.
Claims (18)
1. hydrotreating catalyst, contain boron-containing alumina carrier and at least a VIII of being selected from family and at least a metal component that is selected from group vib, it is characterized in that, described group vib metal component exists with the form of metal oxide, and described VIII family metal component exists with the form of slaine.
2. catalyst according to claim 1, take catalyst as benchmark and with oxide, the content of described VIII family metal component is the 1-10 % by weight, the content of group vib metal component is the 5-40 % by weight.
3. catalyst according to claim 2, take catalyst as benchmark and with oxide, the content of described VIII family metal component is the 1.5-7 % by weight, the content of group vib metal component is the 7-35 % by weight.
4. catalyst according to claim 1 is characterized in that, described group vib metal component is selected from one or more among Cr, Mo, the W, and described VIII family metal component is selected from one or more among Fe, Co, the Ni.
5. catalyst according to claim 4 is characterized in that, described group vib metal is Mo and/or W, and described VIII family metal component is Co and/or Ni.
6. catalyst according to claim 1 is characterized in that, described slaine is selected from the inorganic salts of VIII family metal component or one or more in the organic salt.
7. catalyst according to claim 6 is characterized in that, described inorganic salts are selected from one or more in carbonate, subcarbonate, the nitrate.
8. catalyst according to claim 6 is characterized in that, described organic salt is organic carboxylate.
9. described catalyst is characterized in that according to claim 1-8, and described catalyst also contains one or more auxiliary agents that are selected from phosphorus, fluorine, the silicon, and in element and take catalyst as benchmark, the content of described auxiliary agent is no more than 10 % by weight.
10. described catalyst is characterized in that according to claim 1-8, and described catalyst also contains organic additive, and take described catalyst as benchmark, and in carbon, the content of described organic additive is no more than 10 % by weight.
11. catalyst according to claim 1 is characterized in that, take described carrier as benchmark, the content of boron oxide is the 0.5-10 % by weight in the described boron-containing alumina carrier.
12. catalyst according to claim 11 is characterized in that, take described carrier as benchmark, the content of boron oxide is the 1-7 % by weight in the described boron-containing alumina carrier.
13. the preparation method of a hydrotreating catalyst comprises:
(1) with the solution impregnation boron-containing alumina carrier of the compound that contains the group vib metal, carry out afterwards drying and roasting, the condition of described roasting makes the described compound that contains the group vib metal be enough to be converted into oxide;
(2) product that obtains with the solution impregnation step (1) that contains VIII family slaine carries out drying afterwards, and the condition deficiency of described drying is so that VIII family slaine is decomposed into oxide.
14. method according to claim 11 is characterized in that, the baking temperature of described step (1) is 80-300 ℃, and be 1-12 hour drying time, and described sintering temperature is 350-550 ℃, and roasting time is 2-10 hour; The baking temperature of described step (2) is 30-250 ℃, and be 1-8 hour drying time.
15. method according to claim 12 is characterized in that, the baking temperature of described step (1) is 100-250 ℃, and be 2-8 hour drying time, and described sintering temperature is 400-500 ℃, and roasting time is 3-6 hour; The baking temperature of described step (2) is 60-200 ℃, and be 2-6 hour drying time.
16. method according to claim 11 is characterized in that, described method also comprises introduces the step that is selected from one or more components in phosphorus, fluorine, the silicon.
17. method according to claim 11 is characterized in that, described method also comprises the step of introducing organic additive.
18. a method for hydrotreating hydrocarbon oil is included under the hydrotreatment reaction condition, with hydrocarbon ils and catalyst haptoreaction, it is characterized in that, described catalyst is the described catalyst of claim 1-13 any one.
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| CN108421557A (en) * | 2017-02-15 | 2018-08-21 | 中国石油化工股份有限公司 | Hydrocracking catalyst and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4251350A (en) * | 1979-11-13 | 1981-02-17 | Atlantic Richfield Company | Hydrocarbon hydrotreating process |
| CN1966615A (en) * | 2005-11-16 | 2007-05-23 | 中国石油化工股份有限公司 | Hydrogenation catalyst |
| CN101491766A (en) * | 2008-01-23 | 2009-07-29 | 中国石油化工股份有限公司 | Preparation method of hydrogenation catalyst |
| CN101757931A (en) * | 2008-12-25 | 2010-06-30 | 中国石油化工股份有限公司 | Hydrogenation catalyst, preparation method thereof and hydrocracking method |
| CN102029170A (en) * | 2009-09-28 | 2011-04-27 | 中国石油化工股份有限公司 | Hydrogenation catalyst and preparation method thereof |
-
2012
- 2012-04-26 CN CN2012101252994A patent/CN103372449A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4251350A (en) * | 1979-11-13 | 1981-02-17 | Atlantic Richfield Company | Hydrocarbon hydrotreating process |
| CN1966615A (en) * | 2005-11-16 | 2007-05-23 | 中国石油化工股份有限公司 | Hydrogenation catalyst |
| CN101491766A (en) * | 2008-01-23 | 2009-07-29 | 中国石油化工股份有限公司 | Preparation method of hydrogenation catalyst |
| CN101757931A (en) * | 2008-12-25 | 2010-06-30 | 中国石油化工股份有限公司 | Hydrogenation catalyst, preparation method thereof and hydrocracking method |
| CN102029170A (en) * | 2009-09-28 | 2011-04-27 | 中国石油化工股份有限公司 | Hydrogenation catalyst and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108421557A (en) * | 2017-02-15 | 2018-08-21 | 中国石油化工股份有限公司 | Hydrocracking catalyst and preparation method thereof |
| CN108421557B (en) * | 2017-02-15 | 2020-02-28 | 中国石油化工股份有限公司 | Hydrocracking catalyst and preparation method thereof |
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